Detergent compositions



3,000,832 DETERGENT COMPOSITIONS Pieter L. Kooijman, 'Cornelis Kortland, and Petrus W.

This invention relates to new compositions having detergent properties. More particularly, it pertains to compositions containing synthetic sulfated and sulfonated organic detergents of certain specific types in controlled proporations which have an-exceptionally lvaluable combination of properties.

It has previously been proposed to produce detergent compositions containing synthetic'sulfated'and sulfonated organic detergents of certain kindsfor special purposes. Thus U.S. Patent 2,631,980 claims mixtures'of C -C alkylbenzene sulfonates with C -C alkyl sulfates containing to 30% of the latter to prevent caking of the solid detergent. However, all such previous compositions have certain disadvantages in one or more respects and it is an object of the present inventionto provide new detergent mixtures having improved properties compared with such prior products.

A special object of the invention is the provision of mixtures of alkyl aryl sulfonate detergents and alkyl su1 fate salt detergents which not only have an especially advantageous combination of desirable surface-active properties but also form concentrated solutions in water which are stable to precipitation and gelling at low temperatures and so are eminently adapted for use as liquid detergent compositions. Because of the special advantages of the new detergent mixtures in solutions suitable for sale in the rapidly increasing market for liquid household detergents, for instance,this form of the newcompositions will be emphasized in the following description of the invention, but it will be understood that the new detergent mixtures are not restricted to such use and can be advantageously employed as solid products in powder, flake, bar or other conventional forms.

It has been found that mixtures of alkyl aryl sulfonate detergents and alkyl sulfate salt detergents which satisfy a number of very specific requirements have outstanding surface-active properties combined with a cold stability superior to other mixtures of these detergents. Thus the particular alkyl aryl sulfonate and alkyl sulfate salt detergents of the new compositions when used in the proportions of the invention show synergistic effects especially as regards the cold stability of their solutions.

This cold stability is conveniently measured by clear point determinations, the clear point being the temperature, expressed in degrees centigrade, at which a turbid aqueous solution of the detergent mixture of given concentration clarifies during gradual heating.

The detergent mixtures of the invention having these advantageous properties are mixtures of alkyl aryl sulfonates having 8 and/or 9 carbon atoms in the alkyl groups, preferably together with one or morealkyl aryl sulfonates vw'th 10, ll, 12 or 13 carbon atoms in the alkyl groups and substantially free from alkyl aryl sulfonates comprising less than 8 or more than 13 carbon atoms in the alkyl groups in admixture with mixtures substan- States Patent 0 'stantial amount in such component.

atoms in the molecule in weight ratios between 60:40 and 20:80.

Surprisingly it has been found that the clear point, and foaming andrwetting properties of these alkyl aryl sulfonate-alkyl sulfate salt detergent mixtures can be-improved still further by adding thereto a condensation product of an alkylphenol and ethylene oxide or, in other words, an alkylphenol monoether of polyethylene glycol having 7, 8 or-9 carbon atoms in the alkyl group and 8 to 10 ethylene oxide groups per molecule or a mixture of such alkylphenol ethers. These new'and especially advantageous ternary mixtures are an especially important feature of the invention.

As previously indicated it is essential in order to obtain products with the advantageous properties of the new compositions of the invention, particularly the great reduction in cold point which is desired, that the mixture contain an alkyl aryl sulfonate having either 8 or 9 car-- bon atomsin the group or of a mixture vof such alkyl-aryl sulfonates as the alkyl aryl sulfona'te detergent component of the new detergent mixture or be present in sub- Alkyl aryl sulfona'te's with longer alkyl groups have been found to promote the detergent effect of the mixture and can therefore be added thereto chiefly for this purpose, but alkyl aryl sulfonates with alkyl groups having more than 13 carbon atoms were found .to have an unfavorable eifect.

on the clear point of the mixture, and therefore the mixtures of' the invention should be essentially free from such compounds.

Thus, for example, alkyl aryl sulfonate mixtures with alkyl groups comprising 10 and 11, or 10, 1i and 12, or 1.0, 11, 12 and 13, or 11, 12 and 13, etc., carbon atoms are suitable for use in the present mixtures in addition to the essential C and/or C -alkyl aryl sulfonates. But mixtures of alkyl aryl sulfonates in which the number of carbon atoms in the alkyl groups do not form successive series,and thus, for example, comprise 10 and 12, 10 and 13, 10, 11 and 13 or 11 and 13 carbon atoms, may likewise be used with the C and/or C -alkyl aryl sulfonates with good results.

Alkyl aryl sulfonates which are particularly suitable for use in the process according to the invention may be prepared by alkylation of benzene or naphthalene, or substitution products thereof such as toluene, methyl naphthalene, etc., using HF or H as alkylation catalyst, with an olefin mixture obtained by the vapor-phase cracking of 'paratiin waxes or by cracking by solvent extraction refined catalystically cracked heavy oil, or by polymerization of alkenes such as propene as used for the preparation of propylene tetramers. The olefins used, of course, are those having the number of carbon atoms required to give the above indicated alkyl groups. The alkylate is sulfonated and neutralized in] the customary way. The alkyl sulfates chosen are preferably watersoluble secondary alkyl sulfate salt detergents prepared via sulfation of a mixture substantially consisting of C or C to C olefins obtained in one of the two ways just described. i

Invery many cases the mixtures of compounds to be used for the alkylation and the preparaton of alkyl sulfates will be obtained by distilling mixtures which, in addition, contain compounds with more and/or fewer 's,000,saa

von atoms than the required lower or upper limit, so the mixture of initial material to be used finally rally always contains a small percentage, say approxiely, for example, not more than 5% of compounds I more or fewer carbon atoms than the upper or it limits indicated. bus, for example, a C or C to C olefin mixture Iared in the above manner will virtually always cona small percentage of C and sometimes a number am far fewer, C olefins, and also a small percentage 2 and traces of C olefins. As is usual in practice, ixture of this type is also referred to here as a C or C olefin mixture and the sulfate prepared there- 1 as a C or C to C alkyl sulfate. The same applies he designation of the alkyl aryl sulfonates, so that, example, an alkyl aryl sulfonate mixture referred to he term C or C to C may also contain a small entage of C and C alkyl aryl sulfonates. he preferred alkyl aryl sulfonates are the waterble monoalkylbenzene monosulfonic acid salts, pararly the alkali metal, for instance potassium, or amium or amine salts. Similar salts are preferred in ing the C or C to C alkyl sulfate salt detergent ponent of the new mixtures. These alkyl sulfate are advantageously mixtures predominating in ght or substantially straight chain 2-alkylsulfate salts. greatest improvements in foaming, wetting properties clear point have been obtained by use of ternary rgent mixtures of the previously described polyethylglycol with alkylphenol monoethers with C -C lbenzencmonosodium sulfonates and C -C secondrlkyl sodium sulfates. me amount of alkylphenol-polyethylene glycol monor which should be present with the indicated alkyl sulfonate and alkyl sulfate salt detergent mixtures reparing the preferred compositions of the invention depend upon the properties desired in the final prod- Even relatively small amounts of the specified lphenolpolyethylene glycol monoethers in the new positions give marked improvements in the wetting foaming properties as well as in the clear point of alkylbenzene sulfonate-secondary alkyl sulfate salt rgent mixtures. For instance, a mixture in which letergents are in the proportions, by weight, of apimately 36% C -C alkylbenzene sodium sulfonates, C -C secondary alkyl sodium sulfates, and 10% [phenol polyethylene glycol monoether containing ethylene glycol units, has wetting and foaming :s of 140 and 150, respectively, compared with the I secondary alkyl sodium sulfates taken as 100, the clear point of a 21% w. aqueous solution of the ure is well below 0 C. The foaming properties of mixture exceed that of each of its three detergent :onents. With increasing amounts of the alkylol-polyethylene glycol ethers the wetting and foamiroperties of the mixture increase. ire in which the proportions of the three detergent ionents are 30% C -C alkylbenzene sodium sulzes, 50% C -C secondary alkyl sodium sulfate and octylphenol polyethylene glycol monoether with i ethylene glycol units, the relative wetting and foamalues, on the same basis, are 200 and 160, respec- I, and the clear point is below 0 C. even in soluof 34% concentration. While higher proportions Je used as a general rule it is preferred to employ t 2% to about 30%, more preferably about to t 20% of the specified alkylphenol polyethylene l monoethers based upon the total weight of the detergents used. e new compositions can be prepared by blending her the preformed alkyl aryl sulfonate and alkyl te salt detergents having the required structures, or without the specified alkylphenol polyethylene l monoethers, in the indicated proportions. Advanusly the alkyl aryl sulfonate and alkyl sulfate salt For example, a a

detergents can be produced together by the method of the application of two of us (Kortland and Koonman) with Ferdinand A. Doorman, filed simultaneously herewith. In this method the alkyl sulfate salts are preferably formed by adding the corresponding olefins to the alkyl aryl hydrocarbon sulfonation product andcarrying out sulfation of the olefins with excess sulfonatmgagent present therein. For highest yields the sulfonation 15 carried out with oleum of, for example, 20% free S0 concentration using a mole ratio of S0 to alkyl aryl hydrocarbon of about 5 to 7:1. In a variation of th s process the alkyl aryl sulfonic acids and alkyl sulfuric acids can be separately prepared and mixed together 1B the required ratio, after which the mixture is neutralized and extracted preferably with a liquid hydrocarbon such as gasoline to remove unconverted organic material and/ or other undesirable impurities.

The alkyl aryl sulfonate and alkyl sulfate salt detergents employed in the new compositions will usually contain a. certain amount of inorganic salt, particularly the sulfate corresponding to the base used in the neutralization step in their preparation. It may be desirable to add other builders such as phosphates, silicates, carbonates, foam stabilizers, washing promoters, bleaching agents, and the like, depending upon the intended use of the products. The new compositions can also be used in admixture with other detergents. When the compositions are to be used in solution, for instance sold as liquid detergents, it is desirable that the inorganic salt content be below about 25% and more advantageously not greater than about 15%. The active ingredient content, i.e. the total weight of alkyl aryl sulfonate detergent. alkyl sulfate salt detergent and alkylphenol polyethylene glycol monoethers, in such cases is preferably between about 10% and about 50%. more preferably about 20% to about 40% by weight of the solution.

The invention is further illustrated by the following non-limiting examples.

EXAMPLE I A mixture of alkylbenzene sulfonates, prepared in any of the usual ways, the alkyl groups of which contained 9 to 12 carbon atoms, was mixed in a stirred mixing vessel with C, to C alkyl sulfates in such a ratio that the resulting mixture contained 40 parts by weight of alkylbenzene sulfonates and 60 parts by weight of alkyl sulfates. The clear point of this mixture, which was diluted with water to a 7% concentration, was found to be situated at 1 C. A 40% solution still had a clear point of only 9' C.

EXAMPLEII Benzene was alkylated in a stirred reactor with a C. to C olefin mixture obtained by vapor phase cracking of a catalytically cracked refined heavy hydrocarbon oil.

The alkylation was started with a mixing ratio of benzene to olefins of 10:1. Hydrogen fluoride was used as catalyst, care being taken to ensure a phase ratio of the total quantity of hydrocarbons to hydrogen fluoride of 1:1 by volume. The residence time in the reactor was 30 minutes at room temperature, stirring being carried out at a rate of 220 r.p.m. The pressure was 4 atmospheres absolute.

After the alkylation reaction was complete the excess of benzene was distilled olf at atmospheric pressure. By separating a small quantity of light and heavy ends from the remaining alkylate mixture at 40 mm. Hg, an alkylate avg; obtained which had a sulfonatability not exceeding The alkylate thus prepared was sulfonated at 55' C. with oleum containing 23% by weight of free S0,, starting from a mole ratio of S0,, to alkylate of 6.3:1. Towards the end of the sulfonation reaction there was added to this mixture a quantity of C9 to C olefins which was thus sulfated. The quantity of olefins added was so selected that the resulting mixture contained 40' parts by weight of alkylbenzene sulfonic acids and 60 parts by weight of C to C alkyl sulfuric acid.

The mixture thus obtained was neutralized with a caustic soda solution and saponiiied in order to convert the dialkyl sulfates present into monoalkyl sulfates. After adding 25% by weight of isopropyl alcohol liquid phase desalting was then carried out. An extraction was then carried out with gasoline as a result of which unconverted organic material was removed. Finally, the solution was boiled down until the desired concentration was obtained.

The concentrate prepared in this way was split into three portions which were diluted with water to 20%, 34%, and 40% concentrations, respectively. The clear points thereof were found to be 2 0., 7 C. and 8 C., respectively. v

By applying the variant just described to the process according to the invention it was possible to obtain an improvement in the yield of 15%, calculated on olefins, as compared to the preparation of the same mixture by mixing in the usual way portions of C. to C alkyl aryl sulfonates and C. to C alkyl sulfates preparedseparately.

EXAMPLE III In the following tables the foaming and wetting figures as well as the clear points are given by two mixtures, one comprising a mixture of C, to C secondary alkyl sodium sulfates and C, to C alkylbenzene sodium sulfonates in a weight ratio of 60:40, mixed with octylphenol polyethylene glycol monoether containing 9-9.5 ethylene glycol units in quantities varying from -30% w., while the other comprises a mixture of C to C secondary alkyl sodium sulfates and C to C alkylbenzene sodium sulfonates in a weight ratio of 45:55 also in admixture with octylphenol polyethylene glycol monoether containing 9-9.5 ethylene glycol units in quantities varying from 0-30% w.

The figures given in the tables for the foam and wetting performance are based on those of C to C secondary alkyl sodium sulfates which have been taken to be 100.

When comparing the figures for these compositions having different weight ratios of C to C secondary alkyl sodium sulfates to C to C alkylbenzene sodium sulfates with each other it can he concluded that the foaming being substantially equal for the preparations comprising a similar percentage of the octylphenol polyethylene glycol other, the wetting performance and the clear point where the weight ratio is 45:55 are still better than where the ratio is 60:40.

Other compositions in accordance with the invention which have the previously indicated desirable combination 6 of properties are the following in which the proportior by weight: v

Percent OrOu alkylbensene sodium sulfonate 19 l Og-O anormal-alltyl sodium suliate-. 76 iiiii"tr'i""a"'ntstresri ti; 5

0 one ye ene co at; glycol 152i (a gJmI None p B r y O C a] ltoluene ctassium sulfonate 40. 6 '34. 050:; s condary al yl potassium sulfate... 49. 5 4 Potassium sulfate t 10 s. Heptyl' heucl polyethylene glycol ether with 8 ethylone 3 ycol units None I o I Oi-On aikylbenzeue ammonium sulfonate 43 3 OrC secondary alkyl sodium sulfate.. 29 2 Ammonium sulfate 2 1. Sodium sultate....; 2 l. (l -O; secondary alkylphenol polyethylene glycol with 9.6 ethylene glycol units (avg.) None 2 Octylnaphthalene monosodium sulfonate. 30 25. (Jr-0n secondary alkyl sodium suli'ate 70 s9. Nonylphenol polyethylene glycol other with 10 et yiene glycol units None 1 Cfi-Ofl ulkyltoiuene sodium sulionate... 21. 5 17.1 (I -On secondary alkyl sodium sultat'e- 64. 5 51.1 Sodium suiiate 4 3. 1 Sodium pyrophosphate... l0 1 C7-C9 alkylphcnol polyethylene glycol ether with 9 ethylene glycol units (avg.) None 21 We claim as our invention: 1. A detergent composition forming cold stable aqueous solutions of about 10% to about 50% detergent content, consisting essentially of an alkyl aryl hydrocarbon monosulfonic acid water-soluble salt having an alkyl group of '8 to 9 carbon atoms but essentially free of alkyl aryl sulfonate salts containing alkyl groups of less than 8 and more than 13 carbon atoms, together with a secondary alkyl sulfate salt consisting essentially of a secondary alkyl sulfate water-soluble salt having at least 8 to 9 but not more than 18- carbon-atoms per molecule, said sulfonate and alkyl sulfate'salt being present in a weight ratio of from :40 to 20:80, and an alkyl phenol polyethylene glycol monoether having 7 to 9 carbon atoms in the alkyl group and 8 to 10 ethylene glycol units in the molecule, the amount of said ether being between about 2% and about 30% of the total weight of the detergent composition.

2. A detergent composition in accordance with claim 1 wherein the alkyl aryl sulfonate present in the mixture includes a substantial amount of an alkyl aryl sulfonate having at least 10 but not more than 13 carbon atoms in the alkyl groups.

3. A detergent composition in accordance with claim 1, wherein the alkyl aryl sulfonate is an alkyl monocyclic aromatic hydrocarbon monosulfonic acid water soluble salt.

4. A detergent composition in accordance with claim 1, wherein the alkyl aryl sulfonic acid salt is alkyl benzene sodium sulfonate and the alkyl phenol polyethylene glycol monoether content is between about 10% and about 30% of the total weight of said detergent composition.

5. A detergent composition forming cold stable aqueous solutions of about 10% to about 50% detergent content, consisting essentially of a monoalkylbenzene monosulfonic acid sodium salt'wherein the alkyl group contains 8 to 9 through 13 carbon atoms and a secondary alkyl sulfate sodium salt of 8 to 9 through 18 carbon atoms per molecule which is a predominantly straight chain Z-alkyl sulfate salt, and an alkylphenol polyethylene glycol monoether having 7 to 9 carbon atoms in the alkyl group and 8 to 10- ethylene glycol units, the weight ratio of sulfonate 7 to alkyl sulfate salt being from 60:40 to 20:80 and :ontent of said alkyl phenol ether being about to it 30% of said detergent composition.

A detergent composition in accordance with claim 5, ch each alkyl group of the alkylbcnzene sulfonate alkyl sulfate salt is derived from olefinic products of r phase cracking of parafiinic hydrocarbons.

A liquid detergent composition consisting essentially 'ater, less than about 25% of inorganic salts, and ixture of an alkyl aryl hydrocarbon monosulfonic water-soluble salt having an alkyl group of 8 to 9 m atoms but essentially free of alkyl aryl sulfonate containing alkyl groups of less than 8 and more than arbon atoms and a secondary alkyl sulfate salt cong essentially of a secondary alkyl sulfate water- )le salt having at least 8 to 9 but not more than arbon atoms per molecule, said sulfonate and alkyl te salt being present in a weight ratio of from D to 20:80, and an alkyl phenol polyethylene glycol )ether having 7 to 9 carbon atoms in the alkyl p and 8 to 10 ethylene glycol units in the molecule, \mount of said ether being between about 2% and t 30% of the total weight of the mixture, said mixbeing between about 10% to about 50% by weight e liquid detergent composition.

A liquid detergent composition consisting essentially ater and a ternary mixture consisting of a monoalkyl :ne monosulfonic acid salt wherein the alkyl group contains 8 to 9 through 13 carbon atoms, a secondary alkyl sulfate sodium salt of 8 to 9 through 18 carbon atoms per molecule which is a predominantly straightchain 2-alky1 sulfate salt, and an alkyl phenol polyethylene glycol monoether having 7 to 9 carbon atoms in the alkyl group and 8 to 10 ethylene glycol units, the weight ratio of sulfonate salt to alkyl sulfate salt being from 60:40 to 20:80, and the content of said alkyl phenol ether being about 10% to about of said ternary mixture, said ternary mixture being between about 20% and about by weight of the liquid detergent composition.

References Cited in the file of this patent UNITED STATES PATENTS 2,213,477 Steindorfi et al. Sept. 3, 1940 2,617,772 Keenan Nov. 11, 1952 2,733,212 Epstein et al. Jan. 31, 1956 FOREIGN PATENTS 690,288 Great Britain Apr. 15, 1953 704,687 Great Britain Feb. 24, 1954 727,467 Great Britain Apr. 6, 1955 OTHER REFERENCES Stupel: "Manufacturing Chemist, March 1952, pp. 99-102. 

1. A DETERGENT COMPOSITION FORMING COLD STABLE AQUEOUS SOLUTIONS OF ABOUT 10% TO ABOUT 50% DETERGENT CONTENT, CONSISTING ESSENTIALLY OF AN ALKYL ARYL HYDROCARBON MONOSULFONIC ACID WATER-SOLUBERL SALT HAVING AN ALKYL GROUP OF 8 TO 9 CARBON ATOMS BUT ESSENTIALLY FREE OF ALKYL ARYL SULFONATE SALTS CONTAINING ALKYL GROUPS OF LESS THAN 8 AND MORE THAN 13 CARBON ATOMS, TOGETHER WITH A SECONDARY ALKYL SULFATE SALT CONSISTING ESSENTIALLY OF A SECONDARY ALKYL SULFATE WATER-SOLUBLE SALT HAVING AT LEAST 8 TO 9 BUT NOT MORE THAN 18 CARBON ATOMS PER MOLECULE, SAID SULFONATE AND ALKYL SULFATE SALT BEING PRESENT IN A WEIGHT RATIO OF FROM 60:40 TO 20:80, AND AN ALKYL PHENOL POLYETHYLENE GLYCOL MONOEHTER HAVING 7 TO 9 CARBON ATOMS IN THE ALKYL GROUP AND 8 TO 10 ETHYLENE GLYCOL UNITS IN THE MOLECULE, THE AMOUNT OF SAID ETHER BEING BETWEEN ABOUT 2% AND ABOUT 30% OF THE TOTAL WEIGHT OF THE DETERGENT COMPOSITION. 